Polyprotic Acids

 Some important acids, such as sulfuric acid and phosphoric acid, can
furnish more than one proton per molecule and are called polyprotic acids.
A polyprotic acid always dissociates in a stepwise manner, one proton at a
time.
Carbonic Acid

H2CO3 ↔ H+ + HCO-3 Ka1 = = 4.3 x 10-7

HCO-3 ↔ H+ + CO32- Ka2 = = 4.8 x 10 -11

 The successive Ka values for the dissociation equilibria are designated Ka1
and Ka2 . Note that the conjugate base HCO-3 of the first dissociation
equilibrium becomes the acid in the second step.

1 1
 Phosphoric Acid
 Phosphoric acid is a triprotic acid (three protons) that dissociates in the
following steps:

So the relative acid strengths are H3PO4 >>H2PO4- >>HPO42-

2 2
Example
Calculate the pH of a 5 M H3PO4 solution and determine equilibrium
concentrations of the species H3PO4 , H2PO4-, HPO42- and PO­43.
Solution
The major species in the solution are
H3PO4 and H2O
H3PO4 ↔ H+ + H2PO­4-
Initial 5 0 0

3 3
4
Phosphoric Acid

5 5
 Sulfuric Acid
Sulfuric acid is unique among the common acids because it is a strong
acid in its first dissociation step and a weak acid in its second step:
H2SO4 (aq) → H+ (aq) + HSO4- (aq) Ka1 is very large
HSO4- (aq) ↔ H+ (aq) + SO42- (aq) Ka2 = 1.2 x 10-2

Example
Calculate the pH of a 1.0 M H2SO4 solution.
Solution

6 6
7
In solutions more dilute than 1 M the dissociation of HSO4- is important.
Example
Calculate the pH of a 10-2 M H2SO4 solution. (Invalid approximation)
Solution

8 8
9
10
11